稠杂环化合物研究

稠杂环化合物研究ＸＩ．３－（３′－吡啶基）－６－芳基－均三唑并［３，４－６］－１，３，４－噻二唑的合成张自义，王作祥，郑国钰（兰州大学化学系，７３００００）众所周知，均三唑及１，３，４－噻二唑化合物均具有广泛生物活性，如抗菌￣［１，２］，抗病毒，抗肿...     

含氟芳杂环化合物

一、引言含氟芳杂环化合物是氟化学中一个很有发展潜力的研究领域。由于氟原子和氢原子有相似的原子半径、所以将氟引入到有生物活性的有机化合物中,通常不需改变这些化合物的构型和构象,就能满足受物酶的空间要求,即所谓等几何图形效应(isogeometric     

磷杂环化合物的构象

在有机磷化学中,磷杂环化学是发展得最为迅速的前沿之一。磷杂环化合物不仅可应用于有机合成、工业或农业,而且在医学上也具有潜在的应用前景。总之,磷杂环化合物在国民经济各方面的应用正待开发,其前途是乐观的。     

杂环化合物的羰基化反应

综述了近40年来杂环化合物和一氧化碳在金属络合物催化下的羰基化反应,详细讨论了不同类型反应的有关机理,并展望了该领域的研究前景.     

硼杂环戊二烯化合物研究进展

硼杂环戊二烯(H₄C₄BH)衍生物具有4π电子反芳香性结构和很强的Lewis酸性, 在理论和应用(光电功能材料和烯烃聚合催化剂等)上都有重要研究价值. 综述了近三年来硼杂环戊二烯化合物的研究进展, 着重讨论了其合成、结构和化学反应性, 归纳了硼杂环戊二烯(基)配合物的合成方法与结构类型.     

茂铁杂环化合物的绿色合成

综述了近年来含二茂铁杂环化合物绿色合成研究的新进展, 主要包括微波、超声波、固相合成、特殊催化剂的使用、绿色溶剂、光催化合成等新技术、新试剂在该类反应中的应用.     

也谈杂环化合物的命名

化學十三卷1,2兩期登載了黄新民先生关於雜環化合物命名的意見,又在同誌十三卷4期看到杜作棟先生的意見,在此我想談一談我的一些不成熟的見解。 (一)關於杜作棟先生所提出的幾點 (1)對黄先生命名法不能一望而知為雜     

杂环化合物的光环化加成反应

近廿年来,有机分子的光化学反应已经发展成为有机化学的一个重要而又广阔的分支,像碳环系列一样杂环系列的光化学反应的评论已经广泛报道,本文主要讨论光环化加成反应。 最常遇到的光环化加成反应是[2 2]、[4 4]和[l 2]类型。在这些反应中,杂环化合物既可作为2π组份,又可作为4π组分起反应,而[4 2]和[3 2]类型也是已知的,但以前者更为普遍。     

碘杂环化合物的质谱研究

研究了碘杂环化合物质谱行为和电子碰撞诱导裂解途径.结果表明:3,6-二硝基-二苯并碘六环卤化物(Ⅰ、Ⅱ、Ⅲ)和3,6-二硝基-9-酮-二苯并碘六环卤化物(Ⅳ、Ⅴ、Ⅵ)的EI质谱是样品在仪器内热分解产物的混合质谱;吸附在样品上的溶剂甲酸参与了后者的热分解过程;电子碰撞诱导裂解产生的碎片离子2-卤-2′-碘-4,4′-二硝基-二苯酮(Ⅳ′、V′、Ⅵ′)是化合物Ⅳ、V、Ⅵ的主要热分解产物.     

SOME HETEROCYCLIC PHOSPHOROCHLORIDATES AND THE FORMATION OF OTHER HETEROCYCLIC ORGANOPHOSPHORUS COMPOUNDS

Abstract

Pyrrolidine, morpholine, and β-hydroxyethylmorpholine have been phosphorylated with phosphorus oxychloride, phenylphosphorodichloridate, p-chlorophenylphosphorodichloridate and thiophosphoryl chloride. The resultant phosphorodichloridates have been condensed with a wied range of nucleophilic reagents, e.g. amines, hydrazines, phenols and isobutanol. Piperazine with phosphorus oxychloride (2 mols) gave the N(1) N(4)-diphosphorotetrachloridate, which was characterized as the tetracyclohexylamidate. β-Hydroxyethylpiperazine was similarly phosphorylated to the N,O-diphosphorotetrachloridate which was characterized as the tetraphenylhydrazidate.

Condensation of pyrrolidine (2 mols) with phosphorus oxychloride (1 mol) afforded N,N′-dipyrrolidinophosphorochloridate which was reacted with phenylhydrazide and sodium azide. The phosphoroazide with triphenylphosphine afforded the corresponding triphenylphosphinimine. N-Phenyl N′-pyrrolidinophosphorochloridate with aqueous pyridine gave the corresponding pyrophosphoramide and the stability of the pyrophosphoramide towards hydrolysis was examined. 1,2-Cyclohexanediol was phosphorylated with phenylphosphorodichloridate and thiophosphorylchloride. Trans-4-t-Butylcyclohexyl N,N′-diphenylhydrazinophosphorothioate by reaction with formaldehyde gave a tetra-azaphosphorine P-sulfide. Trans-4-t-Butylcyclohexyl N-phenyl N′-phenylphosphorodiamidic hydrazide reacted with 1,4-dibromobut-2-ene to give a 1,2-diazahex-4-ene.     

CHLOROSULFONATION OF SOME COMPOUNDS CONTAINING TWO PHENYL RINGS

Abstract

Diphenylmethane (1) and dibenzyl (17) reacted with chlorosulphonic acid to give the corresponding p,p′-disulphonyl chlorides (2,18). However, attempted chlorosulfonations of α-chloro-, αα′-dichlorodiphenylmethane, stilbene and 1,4-diphenylbutadiene were unsuccessful.

Diphenylacetic acid reacted with chlorosulfonic acid to give a mixture of 4,4′-dichlorosulfonyl-benzophenone (40) and α-chlorodiphenylmethane-4,4′-disulfonyl chloride (39). Benzilic acid (41) afforded 9-chlorofluorene-2,7-disulfonyl chloride (42), which with amines gave 3 different products according to the reaction conditions. Fluorene (53) and the 9-carboxylic acid (43) have been treated with chlorosulfonic acid. The various sulfonyl chlorides were converted into 43 derivatives for biocidal evaluation. Mechanistic interpretations for the reactions are included.     

CHARACTERIZATION OF SOME SCHIFF BASES OF HETEROCYCLIC COMPOUNDS AND THEIR TRANSITION METAL COMPLEXES

Some new Schiff bases were synthesized by the condensation ofequimolar quantities of salicylaldehyde and 2-amino-5-phenylazo-pyridine orits derivatives in dry benzene(1):Metal complexes of the type ML_2and M'L_3where M=Cu~(2+),Co~(2+),Ni~(2+),Mn~(2+)Pd~(2+),M'=Fe~(3+)and L=different newly synthesizedmonobasic Schiff bases were prepared in absolute ethanolic medium(2)andcharacterized by elementary analysis,conductance measurements,infraredspectra,electronic spectra,magnetic moments studies.     

STUDIES OF HETEROCYCLIC COMPOUNDS: VI1 THE MASS SPECTRA OF SOME 2-THIOPHENEMERCURIC DERIVATIVES

Abstract

The mass spectra of some 2-thiophenemercuric derivatives are determined and the fragmentation interpretations are based on mechanistic analogy and supported in some cases by metastable peaks and low energy mass spectra. They all fragment ultimately to the 2-thienyl cation formed either through a two-step process, by cleavage of Hg[sbnd]X bond to give the 2-thienylmercuric cation, followed by extrusion of mercury, or by a one-step process through cleavage of carbon-mercury bond. Their base peaks being the C₃H₃ ⁺ion (m/e 39).     

一锅合成杂环化合物的新进展

本文综述了最近十年来，利用一锅法合成杂环化合物的进展。参考文献４８篇。     

SYNTHESIS OF SOME NEW HETEROCYCLIC COMPOUNDS FROM BENZOPYRANO[2,3-c]PYRAZOL-3-ONE DERIVATIVES

The reaction of benzopyrano[2,3-c]pyrazol-3-one (1) with some active halo compounds, afforded compounds 4, 8 and 12, respectively. The cyanoethyl derivative 19 was synthesized and treated with active methylenes and sulfur or benzoylisothiocyanate and phenacyl bromide, to give compounds 24_a,b and 27. Compounds 25_a,b and 28 were obtained through the reaction of compounds 24_a,b with acrylonitrile or compound 27 with maleic anhydride. Thiation of compound 1 afforded the corresponding thio derivative 29. The reaction of 4-benzylidene-2-methyloxazolin-5-one with compounds 1 or 29 gave products 30_a,b , respectively.     

D-葡萄糖D-果糖与硼的有机物形成配合物的稳定性研究

葡萄糖异构酶加速葡萄糖与果糖的平衡,平衡时果糖含量为42％左右,体系中加入一些硼酸盐,果糖的含量提高到80％左右,究其原因可能是由于葡萄糖和果糖与硼酸盐形成不同稳定性的配合物。虽然Roy,Conner,Daris,Belcher,Lorand等都已报导了这些配合物的稳定常数,概括结果分歧较大。Belcher曾首次报导了硼酸与D-果糖的配位数为     

BTF变色对其热安定性和与PVB等相容性的影响

通过光照制备了一定量的变色苯并三呋咱氧化物（BTF）,再分别采用差热（DTA）,差示扫描量热（DSC）,真空安定性试验（VST）等热分析方法,对变色前后的BTF进行了热安定性研究及与聚乙烯醇缩丁醛（PVB）等接触材料的相容性研究,并通过热重－红外等仪器分析手段,初步探讨了BTF与PVB之间的作用机理。     

一种耐高温聚噻吩膜的电化学合成

聚噻吩及其衍生物具有高的电导率、良好的环境稳定性以及易于调控的分子链结构,因此一直受到人们的广泛关注．但是,这类材料的耐温性能较差,从而将影响其在有机电子器件中的应用．     

STUDIES IN THE HETEROCYCLIC COMPOUNDS V1. SOME REACTIONS OF 5-CHLORO-2-THIOPHENESULFONYL DERIVATIVES

Abstract

The reactions of 5-chloro-2-thiophenesulfonyl chloride are described. Treatment of the sulfonyl chloride with ammonia, hydrazine hydrate, sodium azide, indole and imidazole gave the sulfonamides (5), sulfonohydrazide (4), sulfonyl azide (3), 1-(5-chloro-2-thiophenesulfonyl)indole (27) and 1-(5-chloro-2-thiophenesulfonyl)-imidazole (26), respectively. The sulfonyl chloride was reacted further with 20 aryl-and cycloalkyl-amines to give the corresponding sulfonamides (6)-(25). Attempted chlorination of the sulfonyl chloride (2) with sulfuryl chloride or bromination of the sulfonyl azide (3) with pyridinium bromide perbromide failed. However, nitration of the sulfonyl chloride (2) with fuming nitric acid gave the 4-nitro-sulfonyl chloride (28), which with sodium azide afforded the 5-chloro-4-nitro-sulfonyl azide (29). The sulfonyl azides, (3) and (29), have been reacted with triphenylphosphine, triethylphosphite, norbornene and cyclohexene. The azides reacted further with indole and 1-methylindole to give the 2-sulfonyl-iminoindolines (34)-(36). The infra-red spectra and mass spectra of some of the substituted thiophenesulfonyl derivatives are discussed.